Floor polish

ABSTRACT

Floor polishes are improved by incorporating therein a fluorochemical which is either an amine salt of a fluorinated cyclic carbinol which has been reacted with phosphorus pentoxide or an amine salt of undecafluorocyclohexane carbinol acrylatemethacrylic acid copolymer.

Umted States Patent 191 [Hi 3,882,067

Petrella 1 May 6, 1975 FLOOR POLISH Primary Examiner-Joseph L. Schofer[75] Inventor: Robert G. Petrella, Glenolden. Pa. Assmam M'Chl Attorney,Agent, or Firm-Barry Moyermzin [73] Assignee: Air Products andChemicals, Inc.,

Allentown, Pa.

[22] Filed: May 17, 1971 (57] ABSTRACT 2 APPL NW 1 4 2 Floor polishesare improved by incorporating therein a fluorochemical which is eitheran amine salt of a fluorinated cyclic carbinol which has been reactedwith [52] U.S. Cl 260/285 R; l06/l0; 260/785;

Int. Cl. C08f 45/52 Field of Search 260/285 R; 106/10 phosphoruspentoxide or an amine salt of undecafluorocyclohexane carbinolacrylate-methacrylic acid copolymer,

12 Claims, N0 Drawings FLOOR POLISH BACKGROUND OF THE INVENTION Thepresent invention relates to polish compositions and, more particularly.to floor polishes containing fluorochemicals which are useful onlinoleum. vinyl. rubher and asphalt floor tile.

In recent years certain fluorochemicals, such as the potassium salt ofpertluorooctanoic acid, have been in corporated into polish compositionsin order to improve the flow and leveling characteristics of floor polishes used to coat floor tiles. When floor polishes are applied to afloor without a fluorochemical, the floor polishes often do not flow outto form a level coating. As a result the coated surface appears to beimperfect with variations in the surface gloss of the treated floortiles. The fluorochemicals which have been used to correct the flow andleveling problems are highly surface active and can cause the formationof bubbles in the applied floor polish. As a result film imperfectionsoccur which mar the appearance and utility of the coated floor tiles.

Typically, polish compositions for use on floors are judged on the basisof their performance as measured by gloss. black heel marking, rubberheel marking. slip, leveling, etc. Although the general appearance ofapolish film is influenced by many factors, the appearance of the polishfilm is most sensitive, Particularly for polishes on light coloredtiles, to dirt pick-up and heel marking. Dirt pick-up occurs when dirtparticles are embedded in a polish film in such a way that they are notremoved by damp mopping. There is a correlation between dirt pick upresistance and the surface energy of the film; the dirt pick-updecreasing as the surface energy of the polish film decreases. Heelmarking can be considered a special case of dirt pick-up whereinmaterial from the shoe heel is transferred to the polished tile in blackstreaks as a consequence of adhesive wear. Once the heel mark isembedded in the polish film, its retention depends, inter alia, on thesurface energy of the film.

There has been a continuing effort to improve both the generalappearance and performance characteris tics of polish films bymodification of floor polish compositions. A significant portion of thiseffort has been directed to the discovery of fluorochemicals which aremore effective than the fluorochemicals presently used, e.g.. C F SON(CHU CH COJQ and are more economical to use.

SUMMARY OF THE INVENTION An object of the present invention is toprovide fluorochemicals which have greater effectiveness than thefluorochemicals presently used in floor polish composition.

Another object of the present invention is to improve both the generalappearance and the performance characteristics of floor polishes.

In accordance with the present invention floor pol ishes are improved bythe incorporation of a fluorochcmical selected from either an amine saltof fluorinutcd cyclic hcxyl carbinol which has been reacted withphosphorus pentoxitle or the amine salt of undecafluorocyclohcxanecarbinol acrylate-methacrylic acid copolymer. The incorporation ofeither lluorochcmical in a floor polish composition is an amount betweenabout 0.01 and about 0.15 solids based on total solids and preferablybetween about 0.02 and about 0.1 solids based on total solids) providesa highly advantageous and unexpected combination of properties, including both good general appearance and improved performancecharacteristics.

DESCRIPTION OF THE PREFERRED EMBODIMENT The fluorochemicals which areincorporated into floor polish compositions in accordance with thepresent invention are either (1 an amine salt of a fluorinated cyclichexyl carbinol which has been reacted with phosphorus pentoxidc or (2)the amine salt of un decafluorocyclohexane carbinol acrylatemethacrylicacid copolymcr.

The method of preparing the first fluorochemical, which can be used inaccordance with the present invention, is disclosed in Ser. No. 39,175,filed May 20, 1970; which application is incorporated by referenceherein. This method involves reducing the material ob' tained by theelectrofiuorination of benzoyl fluoride to a cyclic carbinol materialwhich is subsequently re acted with P 0 and adjusted to a pH of about 5with diethanol amine. The diethanol amine salt of polyfluorocyclohexylalkyl phosphate is prepared in this manner.

The method of preparing the second fluorochemical, which can be used inaccordance with the present in vention, is disclosed in Ser. No.875.590, filed Nov. I0, I969; which application is incorporated byreference herein. The copolymer is prepared by either solution oremulsion copolymcrization and contains a ratio of the fluorocarbonacrylic monomer to the methacrylic acid in the range offrom about 99:Ito about 50:50; preferably from about 9:5 to about :25. Particularlypreferred is the ratio of :15.

The amine salts which can be used include ethyl amine, triethanolamine.ammonium hydroxide. triethylenediamine, diisobutylamine, diethanolamine, ethyl imidazole. imidazole and morpholine.

The floor polish compositions in which the fluorochemicals ofthe presentinvention are incorporated are not critical. The fluorochemicals of thisinvention can be used with any polish whether it be the conventionalalkali sensitive, or acid sensitive or the new detergentresistant.ammonia-sensitive floor polish formulation which results in a surfacewhich is removable using a cleaning solution containing ammonia. Typically, such floor polish formulations contain: (a) an acryliccopolymer. (h) a wax, (c) a leveling agent, (if) a plasti cizer. and (1)a coalescent.

Among the waxes which can be used are those which are dispersible inalkaline aqueous solution. cg. carnauba or a synthetic wax such asalkali dispersible polyethylenes of low molecular weight (around 2.000)oxidized to alkali dispersibility in water, as for instance in thematerial sold under the trade names A-(' Polyethyl ene 629 and EpolcneSuch oxidi/cd material is dis persiblc, for example. in water.containing ammonia at a pH above 7, as at 8 Other waxes that we may useare candelillu. oxidired microcrystalline and preferably mixtures ofthem with carnauba. as in about equal proportions.

Among the film leveling resins which can be used are those which aresoluble in water or dispcrsible therein in presence of alkali and whichcause the film of the dried polish to lie flat after evaporation of theaqueous dispersion thereof. Examples that illustrate the class areshellac; alkali soluble maleic anhydride copolymers with styrene orvinyl ethers such as methyl or ethyl vinyl ether; the products ofhydrolysis of the said maleic anhydride copolymers; the C C alkyl halfesters of the said products of hydrolysis; terpene maleic anhy dridecondensation products; rosin adducts of polyesters. of which estersglycol and glycerin succinates. adipates and maleates are examples; andalkali soluble phenol and formaldehyde condensation products.

Among the plastici7ers which can be employed are carbitol.trilbutoxyethyl) phosphate and the like.

Among the coalescing agents which can be employed are polar organiccompounds which are soluhie in water. including dimethyl sulfoxide.dimethyl formamide. dimethyl acetamide, hexamethylphosphoramide. 2-pyrrolidone and N-methyl2pyrrolidone.

While the exact proportions of the several components to be used areselected in accordance with the specific properties to be emphasized inthe floor polish, generally the acrylic copolymer is present in anamount greater than 60 parts per weight at 15% solids. the wax ispresent in an amount between 2 and 75 parts by weight. the levelingagent is present in an amount less than about l parts by weight. theplasticizer is present in an amount up to about l0 parts by weight andthe coalescent is present in an amount up to about parts by weight.

It will be understood that other ingredients normally found in floorpolish formulations of the type herein described can also beincorporated therein.

Examples of typical formulations include:

Parts by weight The above components are normally added in the orderthey are listed. although this order of addition is not critical. Thecarbitol. ethylene glycol. tri(butoxyethyl) phosphate and fluorochemicalcan be mixed with an equal amount of water and then added slowly to theother ingredients with good stirring. Formaldehyde can also be added inan amount equal to about 500 ppm. as a preservative.

Other typical formulations which can be employed included the following:

Parts by Weight A (lllC'k'l'USSiillkCtl modified acrylic copolymcr whichhas the follomng physlcal properties:

Appearance: Milky liquid Soiids its; 1: I) 5;

-Continued CQIJNI was:

A Zinc-crosslinked modified acrylic copol) rner which has the followingphysical properties:

Appearance: Milky liquid Solids: 38% $0.55! Weight per gallon: 8.7 lbs.pH: 8.5 :05 lonic charge: Anionic (Diluted to l5? solids) Styrcne-malcicanhydridc copolyincr 1 I":

solids in ammonia) Polyethylene wax t 15)? solids in morpholine ole-ate)(arbitol lplasticizer) Ethylene glycol Tri(butoxyethyl) phosphate(plasticizer) Fluorochernical A zinc-crosslinlted modified acryliccopolyrner which has the following physical properties:

Appearance: Milky liquid Solids: 38'); 10.59? Weight per gallon. 8.7lbs. pH: 8.5 t 0.5 Ionic charge: Anionic (Diluted to lSPl solids)Styrcne-maleic anhydridc copolymer Wax emulsion 15; solids) (arbitol(plusticizer) Ethylene glycol Tril butoxyethyl) phosphate (plasticirer)Fluorochemical The invention will be illustrated by the followingspecific examples. it being understood that there is no intention to benecessarily limited by any details thereof since variations can be madewithin the scope of the invention.

EXAMPLE I The floor polish formulations for samples l through 4 wereprepared using the following general formulation:

Item Parts by Weight Rhoplcx 8830 a 1.incerosslinked modifiedacryliccopolymer having the following physical properties:

Appearance; Milky liquid Solids. 385i i 0.5 Weight per gallon. 8.7 lbs.pH: 8.5 i 0.5

lonic charge: Anionic 80.0 (Diluted to l5'il solids) B PolyethyleneLatex l5? solids in morpholine olcatc) i5 0 Sty renc mulcic anhydridccopolymer 1 l5" solids in ammonia) 5.0 D Carhitol (plasticizcr) 3.0 ElPyrrolidone lcoalesccnt) 0.5

TIN hutoxyethyl lphosphate (plasticizer I 0.5 Formalm (37"; ltbacteriostatl ().l5

(varied as shown below for each sample) (1 H Fluoroclicmical A. B. l E"?l or none lcontrol) Items D. E. F and G are mixed with an equal amountof water. stirred vigorously and are then added to items A, B and C.Finally. item H is added to the resulting admixture.

Sample l. 0.5 parts by weight of a V70 aqueous solution of 2. 0.5 partsby weight of a 1% aqueous solution of the ethyl amine salt ofundecafluorocyclohexane carbinol acrylate-methacrylic acid copolymer(Fluorochemical B).

3.0.5 parts by weight ofa 1% aqueous solution of the amine salt of afluorinated cyclic carbinol which has been reacted with phosphoruspentoxide (Fluorochemical C).

4. A control containing no fluorochemical.

Using the following floor service test procedure. which is intended tosimulate actual service conditions and to allow for a determination ofgeneral appearance (including gloss). resistance to soiling. resistanceto heel marking and scuffing. and buff-ability, the compositionsidentified above were evaluated by visual observation.

The test floor panels consist of alternate 9 inch squares of black andwhite vinyl asbestos attached to a backing consisting of a sheet ofaluminum alloy (0.032 inch thick) measuring approximately 36 inchessquare. The aluminum sheet is covered with Kraft paper by taping at theedges. The asphalt tile is attached to the Kraft paper by means ofdouble adhesive faced. pressuresensitive tape. One panel, consisting of16 nine by nine inch tiles. and measuring 36 square inches for the wholepanel. is used for each polish to be tested.

All panels are thoroughly cleaned prior to use with soap and watercontaining a small quantity of aqua ammonia. The panels are thenthoroughly rinsed in clean water and dried before each application oftest polish.

Two coats of polish to be tested are applied to the test floor panel inan amount of approximately L500 square feet per gallon. This isequivalent to using 25 milliliters of wax for each 36 inch square panel.It is spread over the panel with a folded mohair applicator prepared bycutting a strip of mohair 2 inches wide by 5 inches long.

The mohair is folded over a 5 inch long. one-fourth inch diameter glassrod. with the free ends held together with a 5 inch spring clip. Theapplicator is saturated with the polish prior to use and a separateapplicator is used with each polish to be tested. The polish is spreadover the test panels in both directions, using approximately to 12strokes in each direction. and finished off with an additional 10 to 12strokes in the first direction. The panels are allowed to dry for l hourat room temperature and either buffed with a powerdriven brush or notbuffed. Following drying and buffing. the panels are installed in thetest area.

All test floor panels are maintained by daily sweeping and are dampmopped weekly. using clear. cold water. In addition. panels are machinebuffed weekly immediately after damp mopping and drying. The test panelsare shifted one position along the length of the floor every day duringthe test in order to equalize traffic on all panels being used.

The test is continued for a period of 4 weeks. Each week at least threetrained observers rate the test panels for the following properties:

1. Gloss and overall appearance gloss is best evalu ated by judging theappearance of the black tile panels. using approximately the same anglefor viewing in the case of each test panel.

2. Slip resistance this is measured by placing one foot on a piece ofbond paper. placed in front of the other foot at a distance of about 9inches. and sliding the sole of the foot forward along the test area atan angle of about 30to the vertical.

3. Soil resistance this is distinguished from heel and scuff marks. andis considered to be only the embedded soil which shows up on the whitetest panels.

4. Rubber heel marking resistance and scuffing discoloring traffic marksare considered evidence of heel-marking and non-discoloring trafficmarks evidence of scuff marks.

The following method describes the procedure used for the determinationof rubber heel marking on floor finishes. Sample vinyl asbestos whitetiles. 9 inches by 9 inches square. are cleaned by scrubbing with anylon brush and 2% potassium ole-ate solution which contains 0.05% aquaammonia. The tiles are then rinsed with water and dried in air. Thetiles are then flooded with the floor polish to be tested and dried for2 hours in an upright position. Subsequently. the tiles are rotated andonce again flooded with the floor polish. After drying in an uprightposition for 24 hours. the test panels are dried in an environment of77F. and 559? relative humidity.

Six rubber cubes (2 inches by 2 inches by 2 inches) are sanded on eachface very gently with Number 400A carborundum paper. After dusting thesanded cubes. the cubes are loaded together with the coated test panelsin a capsule. The capsule is rotated at 50 rpm for 2.5 minutes and thenthe capsule rotation is reversed for an additional 2.5 minutes. At theend of the 5 minute period, the tiles are removed from the capsule.brushed lightly and rated subjectively from best to worst.

The results of this testing are shown in the following tables where Pstands for poor. F stands for fair. G stands for good. VG stands forvery good. and E stands for excellent.

Ycllowing Continued Sample l 2 3 4 lcontrol) Slip Rcsrstance InitiallyVG VG Vt; W; Attci' first week of tlafi'lc F to G F to G F to G l to GAfter second week oi lltllTII-I P to F F F F After third week of traflicF F F l After fourth week of traffic G F to G G to VG F Soll ResistanceAfter first week of KYLLITIC VG \"G G to VG VG After second week oftrat'ilc G G G G After third week of traffic G G to VG G to VG G to VGAfter fourth week of tl'tllTlt, P to l i F l" Rubber Heel MarkResistance After first week of tram: \"G G to VG \"G to [Z VG Aftersecond week of traffic G to \"(i G G G After third week of traffic G to\'G G to VG G to VG G After fourth week of traffil: F G to \"G G GEXAMPLE ll 20 The fluoroehemicals of the present invention do notEmploying the general floor polish formulation set Causc thfifmmngpmblenls assoclatgd wnh the very forth in Example I.fluorochemicals A. B and C were actwc fluomchemlcals which haveheretofflre incorporated therein in the amounts specified below. usedfluorlflchemlcals of the presenl mvemmn The resulting floor polishformulations were evaluated as are sufficiently acme flow and Y l flgcmsfor fimv and leveling by m6 following pmccdum: 13 Obvlously. manymodlficatlons and variations of the milliliters of the floor polish wasplaced on a (1 inch by mvcmlo as hcrcmheforc Set fonh may be made with"b inch black vinyl tile and spread uniformly over the departing 9mSpirit and SCOPe thereof- Them puma Wih d [5 inch by 15 inch Checscclmhpmi fore, only such llmltatlons should be imposed as are in was thendrawn diagonally from corner to corner m heated b apphinded claimsacrossthe wet tile before the polish was allowed to dry. what Clalmed Thedried polish was then examined visually and rated A POllSh CompositionComprising a CYOSSl-mk for lion and leveling by evaluating how much ofthe X modified acrylic p y i a a leveling was visible and the extent ofdisappearance of the X ntlcnb 1i plustlclicr coakscenl andfluOrOchemlCaL wherein the tluorochernical is selected from the group 35Consisting of an amine salt ofa fluorinated cyclic hexyl carbinolreacted with phosphorus pentoxide and an Humwhcmmfl pmS A B C amine saltof undecafluorocyclohexane carbinol acrylate-methacrylie acidCopolyrner.

i f 4 2. The floor polish composition of claim 1 wherein Rating c a i Uthe t'luoroehemical is an amine salt of a fluorinated cyl T 3 not visiblclic hexyl carbinol reacted with phosphorus pentoxide, i; ;3: 3:55 x' tjj j jl 3. The floor polish composition or claim 2 wherein 4 X dcfinilel}\islhltwith slight ridges the tluorochemical is the diethanol amine saltof fluori- 5 i x 11mm" nated cyclic hexyl carbinol reacted withphosphorus 45 pentoxide.

4. The floor polish composition of claim 1 wherein These results showthat the fluorochemicals of the he fluorochemical is an amine salt ofundecafluorocypresent iniention produce excellent flow and leveling llwml le r in crylate-methacrylic acid copol v characteristics at lowlevels and are superior to the flug0 orochcmical which has become thestandard in the in- Thc floor POI-15h COmPOSiIiOH 0f Claim 4 fB ndustry. the tluorochcmical is the ethyl amine salt of undeca- From theforegoing it will be seen that thi inv i fluorocyclohexane carbinolacrylate-mcthaerylic acid is well adapted to obtain all of the ends andobjects copolymer. herein-above set forth. together with otheradvantages is l fl r Pol h Composition of Claim 1 wherein which areobvious and which are inherent in the sysi the t'luorochemieal ispresent in an amount from about tem. 0.01% to about 015)? soldis basedon total solids.

The present imention provides improved floor pol 7. The lloor polishcomposition of claim 6 wherein ishes for both the domestic andindustrial user. Tough the fluorochemical is present in an amount fromabout and hard tilms are obtained by addition of tluorocarm 0029 toabout (llfi solids based on total solids bolls ill accordance with thepresent invention and 8. A floor polish composition comprising fromabout these tilnls have excellent wear properties a high dc- 0.01"? toabout 0.15); solids based on total solids ot' a gree of resistance todirt pickup and black heel marktluoroehenlical and a polish selectedfrom the group ing good slip resistance. good gloss and good agingconsistlng esselltiall of alkali sensitive acid sensitive propertiesMoreover. lloor polishes made in accorh; and detergent resistant.ammonia sensitive types said dance with the present invention arerccoatable and ma be applied almost immediately over a previous base otthe same floor polish lluorochernical selected from the group consistinges sentially of an amine salt of a tluorinatcd cyclic hexyl carbinolreacted with phosphorous pentoxide and an 1]. The floor polishcomposition of claim 8 wherein the fluorochemical is an amine salt ofundecafluorocyclohexane carbinol acrylate-methacrylic acid copolymer.

12. The floor polish composition of claim ll wherein the fluorochemicalis the ethyl amine salt of undecafluorocyclohexane carbinolacrylate-methacrylic acid copolymer.

1. A FLOOR POLISH COMPOSITION COMPRISING A CROSSLINKABLE MODIFIEDACRYLIC COPOLYMER, A WAX, A LEVELING AGENT, A PLASTICIZER, A COALESCENTAND A FLUOROCHEMICAL, WHEREIN THE FLUOROCHEMICAL IS SELECTED FROM THEGROUP CONSISTING OF AN AMINE SALT OF A FLUORINATED CYCLIC HEXYL CARBINOLREACTED WITH PHOSPHOUS PENTOXIDE AND AN AMINE SALT OFUNDECAFLUOROCYCLOHEXANE CARBINOL ACRYLATE-METHYLACRYLIC ACID COPOLYMER.2. The floor polish composition of claim 1 wherein the fluorochemical isan amine salt of a fluorinated cyclic hexyl carbinol reacted withphosphorus pentoxide.
 3. The floor polish composition of claim 2 whereinthe fluorochemical is the diethanol amine salt of fluorinated cyclichexyl carbinol reacted with phosphorus pentoxide.
 4. The floor polishcomposition of claim 1 wherein the fluorochemical is an amine salt ofundecafluorocyclohexane Carbinol acrylate-methacrylic acid copolymer. 5.The floor polish composition of claim 4 wherein the fluorochemical isthe ethyl amine salt of undecafluorocyclohexane carbinolacrylate-methacrylic acid copolymer.
 6. The floor polish composition ofclaim 1 wherein the fluorochemical is present in an amount from about0.01% to about 0.15% soldis based on total solids.
 7. The floor polishcomposition of claim 6 wherein the fluorochemical is present in anamount from about 0.02% to about 0.1% solids based on total solids.
 8. Afloor polish composition comprising from about 0.01% to about 0.15%solids based on total solids of a fluorochemical and a polish selectedfrom the group consisting essentially of alkali sensitive, acidsensitive and detergent resistant, ammonia sensitive types, saidfluorochemical selected from the group consisting essentially of anamine salt of a fluorinated cyclic hexyl carbinol reacted withphosphorous pentoxide and an amine salt of undecafluorocyclohexanecarbinol acrylate-methacrylic acid polymer.
 9. The floor polishcomposition of claim 8 wherein the fluorochemical is an amine salt of afluorinated cyclic hexyl carbinol reacted with phosphorus pentoxide. 10.The floor polish composition of claim 9 wherein the fluorochemical isthe diethanol amine salt of fluorinated cyclic hexyl carbinol reactedwith phosphorus pentoxide.
 11. The floor polish composition of claim 8wherein the fluorochemical is an amine salt of undecafluorocyclohexanecarbinol acrylate-methacrylic acid copolymer.
 12. The floor polishcomposition of claim 11 wherein the fluorochemical is the ethyl aminesalt of undecafluorocyclohexane carbinol acrylate-methacrylic acidcopolymer.